Unsaturated esters, polyesters, and cross-linked polyesters

ABSTRACT

Novel unsaturated esters and polyesters terminated with alkoxylated phenols and novel cross-linked polyesters formed by reacting these esters and polyesters with a styrene compound. The halogenated cross-linked polyesters are flame retardant.

United States Patent Ford, Jr. Sept. 18, 1973 [54] UNSATURATED ESTERS,POLYESTERS, 2,855,379 10/1958 Heinen 260/861 AND CROSSJJNKED POLYESTERS3,214,491 10/1965 260/871 3,464,852 9/1969 117/1388 Inventori ErnestFord, J Newark, e 3,524,902 8/1970 Feltzin C131. 260/835 [73] Assignee:ICI America, Inc., Wilmington, Del. FOREIGN PATENTS OR APPLICATIONS [22]Filed; Aug. 5, 1970 836,530 6/1960 Great Britain 687,696 6/1964 Canada[21] Appl. No.: 61,170 1,567,721 5/1969 France [52] U S C1 260/869 26 UAOTHER PUBLICATIONS 0 75 51 1m. 01. c0s1121/02 Chem Abstracts12152311964) 58 F' 1d 18 h 260 861, 9, 78.4 l 1 0 can 260/47 {JP/47 L, 1Prir nary Exam1r 1erW1111am H. Short Assistant Examiner-Earl A. Nielsen[56] References Cited Att0rneyKenneth E. Mulford and Roger R. HortonUNITED STATES PATENTS 57 ABSTRACT 3,149,087 '9/1964 Anagnostopoulos eta1. 260/31.6 1 2,726,177 12/1955 Lew 117/161 Novel ated sters andpolyesters termmated 2,765,224 10/1956 Lambrech 71/2.6 with alkoxylatedphenols and novel cross-linked poly- 2,902,518 9/1959 H ardis et a1.260/613 esters formed by reacting these esters and polyesters 3,151,1839/1964 B111 61 3.1. 260/869 a styrene compound The halogenated cross-3,274,293 9/1966 Elfers 613.1 260/869 linked polyesters are fl retardant3,162,615 12/1964 Bremmer 260/47 2,634,251 4/1953 Kass 260/863 X 6Claims, N0 Drawings UNSATURATED ESTERS, POLYESTERS, AND CROSS-LINKEDPOLYESTERS prepared by condensing stoichiometric proportions of anethylenically unsaturated dibasic acid, its anhydride, or mixturesthereof, a diol (optional), and an alkoxylated phenol which may besubstituted. For every two molar proportions of phenol entering thereaction, there are from one to 30 molar proportions of acid oranhydride, and, as required by stoichiometry, from zero to 29 molarproportions of diol; preferably, there are two to molar proportions ofacid or anhydride for every two molar proportions of phenol for higherbromine content in the brominated polyesters. ln practice, if the diolemployed is volatile, more than the stoichiometric amount may be chargedto the reactor to compensate for the amount lost during esterification.If

no diol is employed, the resulting product is the monomericdi(phenoxyalkyl) ester of te dibasic acid, but the preferred productsare polyesters obtained by employing a diol in the range of molarproportions recited above.

' Examples of suitable ethylenically unsaturated dibasic acids includefumaric acid and itaconic acid; maleic anhydride is an example of asuitable ethylenically unsaturated monoanhydride. Fumaric acid andmaleic anhydride are preferred because of their good performance, readyavailability, and economy. Although not preferred, up to about 75 mol ofthe ethylenically unsaturated dibasic acid or its anhydride may bereplaced by a dibasic acid or its anhydride free of ethylenicunsaturation such as phthalic acid, phthalic anhydride, isophthalicacid, succinic acid, or succinic anhydride.

Examples of suitable diols include ethylene glycol, propylene glycol,dipropylene glycol, neopentyl glycol, dibromoneopentyl glycol,diethylene glycol, ethoxylated aniline, trimethyl pentane diol,dipropoxylated Bisphenol A, and diethoxylated Bisphenol A; dipropylcludeoxygen during the reaction cycle. The polyesters may also be prepared byprereacting the dibasic acid or anhydride with the diol followed byreaction with the alkoxylated phenol. Generally, the product will be amixture of esters having various values of n in the general formula. Theacid number of the polyesters of this invention is about five to; acidnumbers below five are difficult to obtain and. above 40 the polyesterhas poor strength properties- The cross-linked polyesters of thisinvention are formed by cross-linking the polyesters of this inventionwith a styrene compound such as styrene, divinyl benzene, or methylstyrene, and chlorinated derivatives thereof; styrene and chlorostyreneare preferred since styrene is inexpensive and chlorostyrene adds to thehalogen content of the polyester. The proportion of polyester to styrenecompound may vary from about one to about three to about three to aboutone; below 25 percent styrene the polyester is too soft and has poorstrength and above 75 percent styrene the polyester is too brittle.

It is preferable to include a second ethylenically unsaturated polyesterduring the cross-linking with the styrene compound to increase thehardness of the resulting cross-linked polyester. Examples of suchsecond polyesters include the maleic acid polyester of propyl ene glycoland the fumaric acid polyester of diethylene glycol. If asecondunsaturated polyester is included, the cross-linked polyesterspreferably comprise about 20 to about 60 percent (by weight) polyesterof this invention, about 20 to about 60 percent styrene compound, andabout 20 to about 50 percent second ethylenically unsaturated polyester.If an ester of this invention is used, an unsaturated polyester isusually employed in order to enhance the physical properties. Thecross-linking reaction is catalyzed with a source of free radicals suchas a peroxide, for-example, benzoyl perene glycol, neopentyl glycol, anddipropoxylated Bisphenol A are preferred because they have a high ratioof carbon to oxygen which enhances the compatibility of the resultingpolyesters with styrene.

The phenol may be substituted with chlorine, bromine, or methyl,preferably bromine since bromine gives superior flame retardancyproperties to the polyester. Up to an average of two atoms of halogen ormethyl may be present per benzene ring; more substitution tends to makethe polyester incompatible with styr'ene. Examples include unsubstitutedphenol, cresols,

- and xylenols; dibromophenol is preferred since it has a maximumbromine content and good. compatibility with styrene. The phenol is thenalkoxylated with about 1 mol to about 3 mols ethylene oxide or propyleneoxide per mol of phenol.

The polyesters may be prepared by mixing approximately stoichiometricproportions of the unsaturated dibasic acid or anhydride, the diol ifpresent, and the alkoxylated phenol together with a polymerizationinhibitor such as about 0.05 to 0.5 percent hydroquinone; a slightexcess of diol may be used to compensate for volatility losses duringesterification. The mixture is heated and stirredand an inert gas suchas nitrogen or carbon dioxide is bubbled through the mixture to exoxideor' methyl ethyl ketone peroxide, following known procedure forpolyester cure. The cross-linked polyesters can be used in a mannersimilar to commer cial polyesters in the manufacture of reinforcedplastics. The halogenated, cross-linked polyesters are flame retardantand will not support combustion; other halogenated compounds or antimonyoxide may be added during polymerization to enhance theirflame-retardant properties. I

The following examples will further illustrate my invention; in all theexamples, 2 mm. vacuum was applied the last two hours of reaction toremove water.-

EXAMPLE 1 EXAMPLE 2 900 g. (3 mols) 1.1 dendro (i.e., alkoxylated with1.1 mols ethylene oxide per mol of phenol) dibromophenol and 174 g. (1.5mols) fumaric acid were reacted inthe presence of 0.2 g. hydroquinonefor 4'hours at C. and l k hours at 200 C. The resulting product was aviscous liquid which analyzed AN 18, SAP 166, OH 26, and percent Br 47,Yield 1,015 g.

EXAMPLE 3 493 g. (1.6 mols) 1.1 prodendro dibromophenol, 135 g. (1.78mols) propylene glycol, and 278 g. (2.4 mols) fumaric acid were reactedin the presence of 0.35 g. hydroquinone for 3 hours at 160 C., 3 hoursat 175 C., and 7 hours at 200 C. The resulting product was a viscousliquid which analyzed AN 13, SAP 333, OH 29, and percent Br 30, Yield804 g.

EXAMPLE 4 720 g. (2.4 mols) 1.1 dendro dibromophenol, 624 g. (2.4 mols)dibromoneopentyl glycol, and 418 g. (3.6 mols) fumaric acid were reactedin the presence of 0.18 g. hydroquinone for 1 hour at 160 C., 2 hours at170 C., 2 hours at 180 C., and 4 hours at 200 C., 22 mm. vacuum beingapplied for the last two hours of reaction. The final product was aviscous liquid which analyzed AN 20, SAP 364, OH 47, and percent Br46.4, Yield 1,620 g.

EXAMPLE 5 418 g. (1.39 mols) 1.1 dendro dibromophenol, 283 g. (1.393mols), 2.5 dendro aniline, and 242 g. (2.09 mols) fumaric acid werereacted in the presence of 0.45 g. hydroquinone for 1 hour at 160 C., 2hours at 175 C. and 5 hours at 200 C., 22 mm. vacuum being applied thelast 2 hours of reaction. The final product, a solid resin, analyzed AN16, SAP 268, OH 41, and percent Br 26.5, Yield 866 g.

EXAMPLE 6 960 g. (3.2 mols) 1.1 dendro dibromophenol, 270 g. (3.55 mols)propylene glycol, and 556 g. (4.79 mols) fumaric acid were reacted inthe presence of 0.8 g. hydroquinone for 3 hours at 160 C., 3 hours at175 C., and 5 hours at 200 C., 22 mm. vacuum being applied the last 2hours of reaction. The resulting product was a viscous liquid whichanalyzed AN 15, SAP 322, OH 37, and percent Br 31, Yield 1,608 g.

EXAMPLE 7 1,105 g. (3.15 mols) 2.2 prodendro Bisphenol A, 832 g. (2.7mols) 1.1 prodendro dibromophenol, and 522 g. (4.5 mols) fumaric acidwere reacted in the presence of 0.16 g. hydroquinone for 3 hours at 180C. and hours at 200 C., 24 mm. vacuum being applied the last 2 hours ofreaction. The resulting product was a solid (M. pt. C 63 B&R) whichanalyzed AN 23, SAP 214, OH 30, and percent Br 19, Yield 2,298 g.

EXAMPLE 8 2,880 g. (9.14 mols) 1.1 prodendro dibromophenol, 762 g. (10mols) propylene glycol, and 1590 g. (13.7 mols) fumaric acid werereacted in the presence of 2.5 g. hydroquinone for 3 hours at 160 C., 3hours at 175 C., and 7 hours at 200 C., 22 mm. vacuum being applied thelast 2 hours of reaction. The resulting product was a viscous liquidwhich analyzed AN 15, SAP 322, OH 29, and percent Br 31, Yield 4,701 g.

EXAMPLE 9 1,291 g. (4.1 mols) 1.1 prodendro dibromophenol, 447 g. (4.3mols) neopentyl glycol, and 714 g. (6.15 mols) fumaric acid were reactedin the presence of 1.2

g. hydroquinone for 3 hours at 160 C., 2 hours'at 180 C., and 6 hours at200 C., 22 mm. vacuum being applied the last 2 hours of reaction. Theresulting product was a viscous liquid which analyzed AN 17, SAP 314, OH29, and percent Br 30, Yield 2,226 g.

EXAMPLE 10 485 g. (1.54 mols) 1.1 prodendro dibromophenol, 236g. (1.62mols) trimethyl pentane diol, and 268 g. (2.31 mols) fumaric acid werereacted in the presence of 0.18 g. hydroquinone for 1 hour at 160 C., 5hours atl C., and 6 hours at 200 C., 22 mm. vacuum being applied thelast 2 hours of reaction. The resulting product was a viscous liquidwhich analyzed AN 23, SAP 288, OH 17, and percent Br 28.6, Yield 886EXAMPLE 1 l 288 g. (2.0 mols) l.l dendro phenol, g. (2.1 mols) ethyleneglycol, and 348 g. (3.0 mols) fumaric acid were reacted in the presenceof 0.38 g. hydroquinone for 10 hours at a top temperature of 200 C.Vacuum was then applied (28 mm.) for 1 hour. The final product, aviscous amber resin, analyzed AN 16, SAP 517, and OH 44, Yield 647 g. A50 percent styrene solution of this polyester on cooling to roomtemperature became pasty due to the crystallinity of the polyester.

EXAMPLE 12 288 g. (2.0 mols) 1.1 dendro phenol, 219 g. (2.1 mols)neopentyl glycol, and 348 g. (3.0 mols) fumaric acid were reacted in thepresence of 0.38 g. hydroquinone for 10 hours at a top temperature of200 C. Vacuum was then applied (28 mm.) for 1 hour. The final product, aviscous amber resin, analyzed AN 17, SAP 461, and OH =39, Yield 737- g.A 50 percent styrene solution of this polyester on cooling to roomtemperature became pasty due to the crystallinity of the polyester.

EXAMPLE 13 288 g. (2.0 mols) 1.1 dendro phenol, g. (2.1 mols) propyleneglycol, and 348 g. (3.0 mols) fumaric acid were reacted in the presenceof 0.35 g. hydroquinone for 14 hours at a top temperature of 200 C.Vacuum was then applied (28 mm.) for 1 hour. The final product, aviscous amber resin, analyzed AN 16, SAP 495, and OH 42, Yield 6,819 g.A 50 percent styrene solution of this polyester on cooling to roomtemperature became pasty on standing.

EXAMPLE 14 EXAMPLE 15 316 g. (2.0 mols) 1.1 prodendro phenol, 130 g.(2.1 mols) ethylene glycol, and 348 g. (3.0 mols) fumaric acid werereacted in the presence of 0.34 g. hydroquinone for 12 hours at a toptemperature of 200 C. Vacuum was then applied (28 mm.) for 1 hour. Thefinal product, a viscous amber resin, analyzed AN 24, SAP 508, and OH30, Yield 672 g. A 50 percent styrene solution of this polyester oncooling to room temperature became pasty on standing.

EXAMPLE 16 991 g. (2.8 mols) 2.2 prodendro Bisphenol A and 406 g. (3.5mols) fumaric acid were reacted in the presence of 0.32 g. hydroquinonefor 5 hours at a top temperature of 210 C. The acid number was found tobe 75. 248 g. (147) mols) 1.1 prodendro o-cresol were then added and thereaction continued at 210 C. until an acid number of 30 was obtained.Vacuum was then applied (28 mm.) for 1 hour. The final product, a solidresin, had a melting point C. (Ball and Ring) of 72 and analyzed AN 19,SAP 253, and OH 32, Yield 1,508 g.

EXAMPLE 17 1,1 18 g. (3.15 mols) 2.2 prodendro Bisphenol A and 406 g.(3.5 mols) fumaric acid were reacted in the presence of 0.32 g.hydroquinone for 3.5 hours at a top temperature of 210C. The acid numberwas found to be 54. 124 g. (0.74 mols) 1.1 prodendro o-cresol were thenadded and the reaction continued until an acid number of 30 wasobtained. Vacuum was then applied (28 mm.) for 1 hour. The finalproduct, a solid resin, had a melting point C. (B&R) of 86 and analyzedAN =16, SAP= 252, and OH 31, Yield 1,514 g.

EXAMPLE 18 1,178 g. (3.32 mols) 2.2 prodendro Bisphenol A and 406 g.(3.5 mols) fumaric acid were reacted in the presence of 0.32 g.hydroquinone for 5.5 hours at a top temperature of 210 C. The acidnumber was found to be 35. 62 g. (0.37 mols) 1.1 prodendro o-cresol werethen added and the reaction continued until an acid number of 30 wasobtained. Vacuum was then applied (28 mm.) for 1 hour. The finalproduct, a solid resin, had a melting C. (B&R) of 96 and analyzed AN 16,SAP 253, and OH 30, Yield 1,518 g.

EXAMPLE 19 1,1 18 g. (3.15 mols) 2.2 prodendro Bisphenol A, 406 g. (3.5mols) fumaric acid, and 124 g. (0.74 mols) 1.1 prodendro o-cresol werereacted in the presence of 0.32 g. hydroquinone for 7 hours at a toptemperature of 210 C. The acid number at this point was 32. Vacuum wasthen applied (28 mm.) and held for 2 hours. The final product, a solidresin, had a melting point C. (B&R) of 86 and analyzed AN =15, SAP= 255,and OH 49, Yield 1,511 g.

The halogenated cross-linked polyesters are useful components of flameretardant polyester systems as shown below. A casting was prepared bymixing the ingredients on a roll mill until the polyester was insolution. Cure of castings was readily effected by use of 1.0 percentbenzoyl peroxide and 0.4 percent dimethyl aniline catalyst system for 18hours at room temperature followed by post-cure of 4 hours at 100 C. Thefollowing Tables give the ingredients (in parts byweight) and theproperties of various compositions:

TABLE 1 Composition A B C ATLAC G-382" 20 20 1O Styrene 20 2OO-Chlorostyrene 40 20 20 Polyester of Exam. 6 4O 40 50 Halogen 23 18 21Viscosity (c.p.s.) 590 240 Gel Time (min..) 25 26 22 Barcol Hardness49-51 46-50 45-50 ASTM 635 NB NB NB l-lLT-15 .80 '90 90 Trademarkpolyester of 2,2-di(4 hydroxy propoxy phenyl) propane. See U.S. Pat. No;2,634,251.

** Non-buming Trademark of Rohm and Haas Co. for a general purposeunsaturated polyester.

**Trademark of Monsanto Co. for chlorinated biphenyl containing 60%chlorine.

TABLE I11 Compositions l .l K L Styrene 30 15 O-Chlorostyrene 20 20 20AROCHLOR 5460 20 l5 10 20 Polyester of Exam. 7 5O 50 Polyester of Exam.10 70 60 Halogen 21 23 27 28 Viscosity (c.p.s.) 360 340 450 320 Gel Time(min.) 15 12 9 l2 Barcol Hardness 38-40 45 45 42 ASTM 635 NB NB NB NBHLT-lS 64 72 100 The polyesters described in Examples 16-18 are ofparticular interest in that they demonstrate that the terminatedpolyesters of this invention have excellent physical properties whencompared to an unterminated polyester made from the same acid and diol.Following are data obtained on their evaluation:

TABLE IV ATLAC Example Example Example G-382 Molar Proportion 16 17 18Control Acid 5.0 5.0 5.0 -5.0 Diol -4.0 4.5 4.75 5.0 1.1 dendro o-cresol2.0 1.0 0.5 0 AN l9 l6 l6 18 SAP 253 252 253 248 OH 32 31 30 35 M. pt.C. (B&R) 72 96 100 Visc. (50% in Styrene op.) 50 l 10 210 500 The aboveresins were cross-linked with 50 percent styrene (50 percent of total),1 percent benzoyl peroxide, and 0.2 percent dimethyl aniline. Thecross-linked polyesters were cured at room temperature followed by 4hours at 100 C. The following casting properties were observed: I

% Elongation What is claimed is: l. A composition comprising a. acondensation reaction product of i. from 2 to mols of an ethylenicallyunsaturated dicarboxylic acid, its anhydride or mixtures thereof,

ii. a diol selected from the group consisting of propylene glycol,dipropylene glycol, neopentyl glycol and dipropoxylated Bisphenol A, and

iii. 2 mols of an alkoxylated dibromophenol wherein said alkoxylateddibromophenol is alkoxylated with from 1 to 3 mols of ethylene oxide orpropylene oxide per mol of dibromophenol and wherein the number of molsof the diol is one less than the number of mols of the acid and an- 8hydride; copolymerized with b. a styrene compound selected from thegroup consisting of styrene and chlorostyrene.

2. A composition as claimed in claim 1, where the ratio of thecondensation reaction product to the styrene compound is about one toabout three to about three to about one.

3. Acomposition as claimed in claim 1, wherein the ethylenicallyunsaturated dicarboxylic acid is fumaric acid.

4. A composition as claimed in claim 1, wherein the anhydride is maleicanhydride.

5. A composition as claimed in claim 1 wherein up to about mol percentof the ethylenically unsaturated dicarboxylic acid, its anhydride, ormixtures thereof is replaced by a dicarboxylic acid or its anhydridefree of ethylenic unsaturation and selected from the group consisting ofphthalic acid, phthalic anhydride, isophthalic acid, succinic acid, orsuccinic anhydride.

6. A composition as claimed in claim 1 comprising about 20 to about 60percent the condensation reaction product, about 20 to about 60 percentstyrene compound, and about 20 to about 50 percent of an ethylenicallyunsaturated polyester.

my UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 rDated -In ventor(s) Ernest C. Ford, Jr.

It-is' certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 1, line -23, "te". should read --the- Column 5 line 15,(l47)mols) should read 1 mols) Column 6, line 13, "*Trademark" shouldread --*Trademark of Atlas Chemical lndustrles, Inc., for fumaric acid-Signed end sealed this 3rd day of December 1974.

(SEAL) Attest: r

McCOY M. GIBSON JR v o. MARSHALL DANN Arresting Officer Commissioner ofPatents

2. A composition as claimed in claim 1, where the ratio of thecondensation reaction product to the styrene compound is about one toabout three to about three to about one.
 3. A composition as claimed inclaim 1, wherein the ethylenically unsaturated dicarboxylic acid isfumaric acid.
 4. A composition as claimed in claim 1, wherein theanhydride is maleic anhydride.
 5. A composition as claimed in claim 1wherein up to about 75 mol percent of the ethylenically unsaturateddicarboxylic acid, its anhydride, or mixtures thereof is replaced by adicarboxylic acid or its anhydride free of ethylenic unsaturation andselected from the group consisting of phthalic acid, phthalic anhydride,isophthalic acid, succinic acid, or succinic anhydride.
 6. A compositionas claimed in claim 1 comprising about 20 to about 60 percent thecondensation reaction product, about 20 to about 60 percent styrenecompound, and about 20 to about 50 percent of an ethylenicallyunsaturated polyester.